Cyclopropyl-anellated 3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles

ABSTRACT

Cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formula Iin which the variables are as defined in the description, and their agriculturally useful salts are described. The compounds have herbicidal action.

The present invention relates to certain cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles and tointermediates and processes for their preparation, to compositionscomprising them and to the use of these derivatives or compositionscomprising them for controlling harmful plants.

The literature, for example WO 96/26206, WO 98/31682 and WO 98/31681,discloses pyrazol-4-yl-benzoyl derivatives.

The earlier applications WO 00/34273, WO 00/34272, DE 19936520.2 and DE19936518.0 describe, inter alia, (4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles and their herbicidal properties. Derivatives havingfused cycloalkane rings have not been described.

However, the herbicidal properties of the prior-art compounds and theircompatibility with crop plants are not entirely satisfactory.

It is an object of the present invention to provide novel, in particularherbicidally active, compounds having improved properties.

We have found that this object is achieved by the cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formulaI

in which

R¹ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,halogen or nitro;

R² is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy,C₁-C₆-alkylthio, C₁-C₆-haloalkylthio, C₁-C₆-alkylsulfinyl,C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆-haloalkylsulfonyl,halogen, cyano or nitro;

R³ is hydrogen, C₁-C₆-alkyl or halogen;

R⁴ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;

R⁵ may have the meanings given for R⁴; or

R⁴, R⁵ together are a C₁-C₄-alkanediyl group which may be partially orfully halogenated and/or may carry one to three C₁-C₄-alkyl groups;

R⁶ is hydroxyl, C₁-C₆-alkoxy, C₃-C₆-alkenyloxy, C₁-C₆-alkylsulfonyloxy,C₁-C₆-alkylcarbonyloxy, phenyl-C₁-C₄-alkoxy,phenylcarbonyl-C₁-C₄-alkoxy, phenylsulfonyloxy, phenylcarbonyloxy, wherethe phenyl radical of the four lastmentioned substituents may bepartially or fully halogenated and/or may carry one to three of thefollowing groups: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C_(l)-C₄-alkoxy or C₁-C₄-haloalkoxy;

R⁷ is hydrogen, C₁-C₆-alkyl or cyclopropyl;

R⁸ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl; and their agriculturallyuseful salts.

Furthermore, we have found herbicidal compositions which comprise thecompounds I and have very good herbicidal activity. Moreover, we havefound processes for preparing these compositions and methods forcontrolling undesirable vegetation using the compounds I.

Depending on the substitution pattern, the compounds of the formula Imay contain one or more centers of chirality, in which case they arepresent as enantiomer or diastereomer mixtures. The invention providesboth the pure enantiomers or diastereomers and their mixtures.

The compounds of the formula I can also be present in the form of theiragriculturally useful salts, the nature of the salt generally beingimmaterial. In general, the salts of those cations and the acid additionsalts of those acids are suitable whose cations and anions,respectively, do not adversely affect the herbicidal action of thecompounds I.

Suitable cations are, in particular, ions of the alkali metals,preferably lithium, sodium and potassium, the alkaline earth metals,preferably calcium and magnesium, the transition metals, preferablymanganese, copper, zinc and iron, and also ammonium where, if desired,one to four hydrogens may be replaced by C₁-C₄-alkyl,hydroxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl, preferably ammonium,dimethylammonium, diisopropylammonium, tetramethylammonium,tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium,di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, furthermorephosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium,and sulfoxonium ions, preferably tri (C₁-C₄-alkyl) sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide,fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogenphosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate,hexafluorophosphate, benzoate and the anions of C₁-C₄-alkanoic acids,preferably formate, acetate, propionate and butyrate.

The organic moieties mentioned for the substituents R¹-R8 or as radicalson phenyl rings are collective terms for individual enumerations of theindividual group members. All hydrocarbon chains, i.e. all alkyl,alkylcarbonyl, haloalkyl, alkoxy, haloalkoxy, alkylcarbonyloxy,alkylsulfonyloxy, alkylthio, haloalkylthio, alkylsulfinyl,haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl,alkenyloxy, phenylalkyl, phenylcarbonylalkyl, phenylalkoxy andphenylcarbonylalkoxy moieties can be straight-chain or branched. Unlessindicated otherwise, halogenated substituents preferably carry one tofive identical or different halogen atoms. The term halogen denotes ineach case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

C₁-C₄-alkyl, and the alkyl moieties of C₁-C₄-alkylcarbonyl,C₁-C₄-alkylcarbonyloxy, phenyl-C₁-C₄-alkyl andphenylcarbonyl-C₁-C₄-alkyl: for example methyl, ethyl, propyl,1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and1,1-dimethylethyl;

C₁-C₆-alkyl, and the alkyl moieties of C₁-C₆-alkylcarbonyl andC₁-C₆-alkylcarbonyloxy: C₁-C₄-alkyl as mentioned above, and also, forexample, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl,1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-3-methylpropyl;

C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, i.e., for example, chloromethyl, dichloromethyl,trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,bromomethyl, iodomethyl, chlorofluoromethyl, dichlorofluoromethyl,chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl,2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl,2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl,3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl,2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyland nonafluorobutyl;

C₁-C₆-haloalkyl: C₁-C₄-haloalkyl as mentioned above, and also, forexample, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl,undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl,6-iodohexyl or dodecafluorohexyl;

C₁-C₂-alkoxy as alkoxy moieties of phenyl-C₁-C₂-alkoxy andphenylcarbonyl-C₁-C₂-alkoxy: methoxy and ethoxy;

C₁-C₄-alkoxy, and the alkoxy radicals of phenyl-C₁-C₄-alkoxy andphenylcarbonyl-C₁-C₄-alkoxy: C₁-C₂-alkoxy as mentioned above, and also,for example, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy,2-methylpropoxy and 1,1-dimethylethoxy;

C₁-C₆-alkoxy: C₁-C₄-alkoxy as mentioned above, and also, for example,pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy,1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy,1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy,3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy,1,2-dimethylbutoxy,1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy,3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy,1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxyand 1-ethyl-2-methylpropoxy;

C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, i.e., for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy,2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy,2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy,3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy,3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy,2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy,1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy,4-bromobutoxy and nonafluorobutoxy;

C₁-C₆-haloalkoxy: C₁-C₄-haloalkoxy as mentioned above, and also, forexample, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy,5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy,6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy;

C₁-C₄-alkylthio: for example methylthio, ethylthio, propylthio,1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and1,1-dimethylethylthio;

C₁-C₆-alkylthio: C₁-C₄-alkylthio as mentioned above, and also, forexample, pentylthio, 1-methylbutylthio, 2-methylbutylthio,3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio,1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio,2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio,1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio,2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio,1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio or1-ethyl-2-methylpropylthio;

C₁-C₄-haloalkylthio: a C₁-C₄-alkylthio radical as mentioned above whichis partially or fully substituted by fluorine, chlorine, bromine and/oriodine, i.e., for example, fluoromethylthio, difluoromethylthio,trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio,2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio,2,2-difluoroethylthio, 2,2,2-trifluoroethylthio,2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio,2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio,2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio,3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio,2,3-dichloropropylthio, 3,3,3-trifluoropropylthio,3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio,heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio,1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio,4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio andnonafluorobutylthio;

C₁-C₆-haloalkylthio: C₁-C₄-haloalkylthio as mentioned above, and also,for example, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio,5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio,6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio ordodecafluorohexylthio;

C₁-C₆-alkylsulfinyl (C₁-C₆-alkyl-S(═O)—): for example methylsulfinyl,ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl,1-methylpropylsulfinyl, 2-methylpropylsulfinyl,1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl,2-methylbutylsulfinyl, 3-methylbutylsulfinyl,2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl,1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl,1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl,4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl,1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl,2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl,3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl,11,12-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl,1-ethyl-1-methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl;

C₁-C₆-haloalkylsulfinyl: C₁-C₆-alkylsulfinyl as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, i.e., for example, fluoromethylsulfinyl, difluoromethylsulfinyl,trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl,bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl,2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl,2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl,2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl,2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl,pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl,3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl,2-bromopropylsulfinyl, 3-bromopropylsulfinyl,2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl,2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl,3,3,3-trichloropropylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl,heptafluoropropylsulfinyl, 1-(fluoromethyl)-2-fluoroethylsulfinyl,1-(chloromethyl)-2-chloroethylsulfinyl,1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl,4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, nonafluorobutylsulfinyl,5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl,5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl,6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl ordodecafluorohexylsulfinyl;

C₁-C₄-alkylsulfonyl (C₁-C₄-alkyl-S(═O)₂—), and the alkylsulfonylmoieties of C₁-C₄-alkylsulfonyloxy: for example methylsulfonyl,ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl,1-methylpropylsulfonyl, 2-methylpropylsulfonyl and1,1-dimethylethylsulfonyl;

C₁-C₆-alkylsulfonyl, and the alkylsulfonyl moieties ofC₁-C₆-alkylsulfonyloxy: a C₁-C₄-alkylsulfonyl radical as mentionedabove, and also, for example, pentylsulfonyl, 1-methylbutylsulfonyl,2-methylbutylsulfonyl, 3-methylbutylsulfonyl,1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl,2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl,1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl,4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl,1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl,2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl,3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl,1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl,1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;

C₁-C₆-haloalkylsulfonyl: a C₁-C₆-alkylsulfonyl radical as mentionedabove which is partially or fully substituted by fluorine, chlorine,bromine and/or iodine, i.e., for example, fluoromethylsulfonyl,difluoromethylsulfonyl, trifluoromethylsulfonyl,chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl,2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl,2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl,2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl,2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl,2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl,2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl,3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl,2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl,2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl,3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl,heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl,1-(chloromethyl)-2-chloroethylsulfonyl,1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl,4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl,5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl,5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl,6-iodohexylsulfonyl or dodecafluorohexylsulfonyl;

C₃-C₆-alkenyloxy: for example prop-1-en-1-yloxy, prop-2-en-1-yloxy,1-methylethenyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yloxy,1-methyl-prop-1-en-1-yloxy, 2-methylprop-1-en-1-yloxy,1-methylprop-2-en-1-yloxy, 2-methylprop-2-en-1-yloxy, penten-1-yloxy,penten-2-yloxy, penten-3-yloxy, penten-4-yloxy,1-methylbut-1-en-1-yloxy, 2-methylbut-1-en-1-yloxy,3-methylbut-1-en-1-yloxy, 1-methyl-but-2-en-1-yloxy,2-methylbut-2-en-1-yloxy, 3-methylbut-2-en-1-yloxy,1-methylbut-3-en-1-yloxy, 2-methylbut-3-en-1-yloxy,3-methylbut-3-en-1-yloxy, 1,1-dimethylprop-2-en-1-yloxy,1,2-dimethylprop-1-en-1-yloxy, 1,2-dimethylprop-2-en-1-yloxy,1-ethylprop-1-en-2-yloxy, 1-ethylprop-2-en-1-yloxy, hex-4-en-1-yloxy,hex-2-en-1-yloxy, hex-3-en-1-yloxy, hex-4-en-m-yloxy, hex-5-en-1-yloxy,1-methylpent-1-en-1-yloxy, 2-methylpent-1-en-1-yloxy,3-methylpent-2-en-1-yloxy, 4-methylpent-2-en-1-yloxy,3-methylpent-2-en-1-yloxy, 2-methylpent-2-en-1-yloxy,3-methylpent-2-en-1-yloxy, 4-methylpent-2-en-1-yloxy,1-methylpent-3-en-1-yloxy, 2-methylpent-3-en-1-yloxy,3-methylpent-3-en-1-yloxy, 4-methylpent-3-en-1-yloxy,1-methylpent-4-en-1-yloxy, 2-methylpent-4-en-1-yloxy,3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-1-yloxy,1,2-dimethylbut-2-en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy,1,2-dimethylbut-1-en-1-yloxy, 1,2-dimethylbut-2-en-1-yloxy,1,2-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy,1,3-dimethylbut-2-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy,2,2-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy,2,3-dimethylbut-2-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy,3,3-dimethylbut-1-en-1-yloxy, 3,3-dimethylbut-2-en-1-yloxy,1-ethylbut-3-en-1-yloxy, 1-ethylbut-2-en-1-yloxy,2-ethylbut-3-en-1-yloxy, 2-ethylbut-3-en-1-yloxy,2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy,1,1,2-trimethylprop-2-en-1-yloxy, 1-ethyl-1-methylprop-2-en-1-yloxy,1-ethyl-2-methylprop-1-en-1-yloxy and1-ethyl-2-methyl-prop-2-en-1-yloxy;

C₃-C₆-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl,buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl,2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl,penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl,1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl,1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl,1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl,1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl,hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl,2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl,4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl,2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl,1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl,2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl,3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl,1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;

C₁-C₄-alkanediyl: for example methanediyl, 1,2-ethanediyl,1,3-propanediyl and 1,4-butanediyl.

The phenyl rings of the radicals phenylalkyl, phenylcarbonylalkyl,phenylalkoxy, phenylcarbonylalkoxy, phenylsulfonyl, phenylsulfonyloxy,phenylcarbonyl and phenylcarbonyloxy are preferably unsubstituted orcarry one, two or three halogen atoms and/or one nitro group, one cyanogroup, one or two methyl, trifluoromethyl, methoxy or trifluoromethoxygroups.

In the formula I,

R¹ is preferably C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy or halogen;

in particular C₁-C₄-alkyl, preferably methyl, ethyl, n-propyl orisopropyl; or halogen, preferably fluorine, chlorine or bromine;

particularly preferably methyl or chlorine;

most preferably methyl;

R² is preferably C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl, halogen or nitro;

in particular C₁-C₄-haloalkyl, preferably difluoromethyl ortrifluoromethyl; C₁-C₄-alkylsulfonyl, preferably methylsulfonyl orethylsulfonyl; or halogen, preferably fluorine or chlorine;

particularly preferably C₁-C₄-alkylsulfonyl, most preferablymethylsulfonyl;

R³ is preferably hydrogen, C₁-C₄-alkyl or halogen;

in particular hydrogen, chlorine or methyl;

particularly preferably hydrogen;

R⁴ is preferably hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;

in particular hydrogen, methyl, ethyl, chloromethyl or bromomethyl;

R⁵ is preferably hydrogen or C₁-C₄-alkyl;

in particular hydrogen; or

R⁴,R⁵ together are preferably a C₁-C₄-alkanediyl group;

in particular a methanediyl group;

particularly preferably are hydrogen; or

R⁶ is preferably hydroxyl, C₁-C₆-alkoxy, C₁-C₆-alkylsulfonyloxy,C₁-C₆-alkylcarbonyloxy, phenyl-C₁-C₂-alkoxy,phenylcarbonyl-C₁-C₂-alkoxy, phenylsulfonyloxy, phenylcarbonyloxy, wherethe phenyl radical of the four lastmentioned substituents may bepartially or fully halogenated and/or may carry one to three of thefollowing groups: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy;

in particular hydroxyl, phenyl-C₁-C₂-alkoxy,phenylcarbonyl-C₁-C₂-alkoxy, phenylsulfonyloxy, phenylcarbonyloxy, wherethe phenyl radical of the four lastmentioned substituents may bepartially or fully halogenated or may carry one to three of thefollowing groups: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy;

particularly preferably hydroxyl;

R⁷ is preferably hydrogen, C₁-C₄-alkyl or cyclopropyl; in particularC₁-C₄-alkyl, preferably methyl, ethyl, isopropyl, isobutyl, s-butyl ort-butyl; or cyclopropyl;

R⁸ is preferably hydrogen or C₁-C₄-alkyl;

in particular hydrogen, methyl or ethyl;

particularly preferably hydrogen or methyl.

Particular preference is given to cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formulaI in which

R¹ is C₁-C₆-alkyl or halogen;

R² is C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl or halogen;

R³ is hydrogen, C₁-C₄-alkyl or halogen;

R⁷ is C₁-C₄-alkyl or cyclopropyl;

R⁸ is hydrogen or C₁-C₄-alkyl.

Particular preference is furthermore given to cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formulaI in which

R¹ is methyl or chlorine;

R² is C₁-C₄-alkylsulfonyl;

R³ is hydrogen, methyl or chlorine;

R⁴ is hydrogen, methyl, ethyl, chloromethyl or bromomethyl;

R⁵ is hydrogen or methyl;

in particular is hydrogen; or

R⁴,R⁵ together form a methanediyl group;

R⁶ is hydroxyl;

R⁷ is C₁-C₄-alkyl or cyclopropyl;

R⁸ is hydrogen or C₁-C₄-alkyl.

Extraordinary preference is given to the compounds of the formula Ia1(≡I where R³, R⁸=H; R⁶=OH; R⁷=CH₃), in particular to the compounds Ia1.1to Ia1.77 of Table 1, where the definitions of the radicals R¹ to R⁸ areof particular importance for the compounds according to the inventionnot only in combination with one another but also in each case on theirown.

TABLE 1 Ia1

No. R¹ R² R⁴ R⁵ Ia1.1 Cl SO₂CH₃ H H Ia1.2 Cl SO₂CH₃ CH₃ H Ia1.3 ClSO₂CH₃ CH₃ CH₃ Ia1.4 Cl SO₂CH₃ CH₂CH₃ H Ia1.5 Cl SO₂CH₃ CH₂Cl H Ia1.6 ClSO₂CH₃ CH₂F H Ia1.7 Cl SO₂CH₃ CH₂Br H Ia1.8 Cl SO₂CH₃ CF₃ H Ia1.9 ClSO₂CH₃ CHClCH₃ H Ia1.10 Cl SO₂CH₃ CHFCH₃ H Ia1.11 Cl SO₂CH₃ CH₂ Ia1.12CH₃ SO₂CH₃ H H Ia1.13 CH₃ SO₂CH₃ CH₃ H Ia1.14 CH₃ SO₂CH₃ CH₃ CH₃ Ia1.15CH₃ SO₂CH₃ CH₂CH₃ H Ia1.16 CH₃ SO₂CH₃ CH₂Cl H Ia1.17 CH₃ SO₂CH₃ CH₂F HIa1.18 CH₃ SO₂CH₃ CH₂Br H Ia1.19 CH₃ SO₂CH₃ CF₃ H Ia1.20 CH₃ SO₂CH₃CHClCH₃ H Ia1.21 CH₃ SO₂CH₃ CHFCH₃ H Ia1.22 CH₃ SO₂CH₃ CH₂ Ia1.23 Cl CF₃H H Ia1.24 Cl CF₃ CH₃ H Ia1.25 Cl CF₃ CH₃ CH₃ Ia1.26 Cl CF₃ CH₂CH₃ HIa1.27 Cl CF₃ CH₂Cl H Ia1.28 Cl CF₃ CH₂F H Ia1.29 Cl CF₃ CH₂Br H Ia1.30Cl CF₃ CF₃ H Ia1.31 Cl CF₃ CHClCH₃ H Ia1.32 Cl CF₃ CHFCH₃ H Ia1.33 ClCF₃ CH₂ Ia1.34 CH₃ CF₃ H H Ia1.35 CH₃ CF₃ CH₃ H Ia1.36 CH₃ CF₃ CH₃ CH₃Ia1.37 CH₃ CF₃ CH₂CH₃ H Ia1.38 CH₃ CF₃ CH₂Cl H Ia1.39 CH₃ CF₃ CH₂F HIa1.40 CH₃ CF₃ CH₂Br H Ia1.41 CH₃ CF₃ CF₃ H Ia1.42 CH₃ CF₃ CHClCH₃ HIa1.43 CH₃ CF₃ CHFCH₃ H Ia1.44 CH₃ CF₃ CH₂ Ia1.45 CH₂CH₃ SO₂CH₃ H HIa1.46 CH₂CH₃ SO₂CH₃ CH₃ H Ia1.47 CH₂CH₃ SO₂CH₃ CH₃ CH₃ Ia1.48 CH₂CH₃SO₂CH₃ CH₂CH₃ H Ia1.49 CH₂CH₃ SO₂CH₃ CH₂Cl H Ia1.50 CH₂CH₃ SO₂CH₃ CH₂F HIa1.51 CH₂CH₃ SO₂CH₃ CH₂Br H Ia1.52 CH₂CH₃ SO₂CH₃ CF₃ H Ia1.53 CH₂CH₃SO₂CH₃ CHClCH₃ H Ia1.54 CH₂CH₃ SO₂CH₃ CHFCH₃ H Ia1.55 CH₂CH₃ SO₂CH₃ CH₂Ia1.56 CH₃ SO₂CH₂CH₃ H H Ia1.57 CH₃ SO₂CH₂CH₃ CH₃ H Ia1.58 CH₃ SO₂CH₂CH₃CH₃ CH₃ Ia1.59 CH₃ SO₂CH₂CH₃ CH₂CH₃ H Ia1.60 CH₃ SO₂CH₂CH₃ CH₂Cl HIa1.61 CH₃ SO₂CH₂CH₃ CH₂F H Ia1.62 CH₃ SO₂CH₂CH₃ CH₂Br H Ia1.63 CH₃SO₂CH₂CH₃ CF₃ H Ia1.64 CH₃ SO₂CH₂CH₃ CHClCH₃ H Ia1.65 CH₃ SO₂CH₂CH₃CHFCH₃ H Ia1.66 CH₃ SO₂CH₂CH₃ CH₂ Ia1.67 Cl SO₂CH₂CH₃ H H Ia1.68 ClSO₂CH₂CH₃ CH₃ H Ia1.69 Cl SO₂CH₂CH₃ CH₃ CH₃ Ia1.70 Cl SO₂CH₂CH₃ CH₂CH₃ HIa1.71 Cl SO₂CH₂CH₃ CH₂Cl H Ia1.72 Cl SO₂CH₂CH₃ CH₂F H Ia1.73 ClSO₂CH₂CH₃ CH₂Br H Ia1.74 Cl SO₂CH₂CH₃ CF₃ H Ia1.75 Cl SO₂CH₂CH₃ CHClCH₃H Ia1.76 Cl SO₂CH₂CH₃ CHFCH₃ H Ia1.77 Cl SO₂CH₂CH₃ CH₂

Extraordinary preference is also given to the compounds of the formulaIa2, in particular to the compounds Ia2.1 to Ia2.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁷ is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa3, in particular to the compounds Ia3.1 to Ia3.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁷ is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa4, in particular to the compounds Ia4.1 to Ia4.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁷ is t-butyl.

Extraordinary preference is also given to the compounds of the formulaIa5, in particular to the compounds Ia5.1 to Ia5.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁷ is cyclopropyl.

Extraordinary preference is also given to the compounds of the formulaIa6, in particular to the compounds Ia6.1 to Ia6.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁸ is methyl.

Extraordinary preference is also given to the compounds of the formulaIa7, in particular to the compounds Ia7.1 to Ia7.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁸ is methyl and R⁷is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa8, in particular to the compounds Ia8.1 to Ia8.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁸ is methyl and R⁷is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa9, in particular to the compounds Ia9.1 to Ia9.77, which differ fromthe corresponding compounds Ia1.1 to Ia1.77 in that R⁸ is methyl and R⁷is t-butyl.

Extraordinary preference is also given to the compounds of the formulaIa10, in particular to the compounds Ia10.1 to Ia10.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁸ is methyland R⁷ is cyclopropyl.

Extraordinary preference is also given to the compounds of the formulaIa11, in particular to the compounds Ia11.1 to Ia11.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ isphenylcarbonyloxy.

Extraordinary preference is also given to the compounds of the formulaIa12, in particular to the compounds Ia12.1 to Ia12.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ isphenylcarbonyloxy and R⁷ is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa13, in particular to the compounds Ia13.1 to Ia13.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ isphenylcarbonyloxy and R⁷ is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa14, in particular to the compounds Ia14.1 to Ia14.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ isphenylcarbonyloxy and R⁷ is t-butyl.

Extraordinary preference is also given to the compounds of the formulaIa15, in particular to the compounds Ia15.1 to Ia15.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-fluorophenylcarbonyloxy.

Extraordinary preference is also given to the compounds of the formulaIa16, in particular to the compounds Ia16.1 to Ia16.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-fluorophenylcarbonyloxy and R⁷ is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa17, in particular to the compounds Ia17.1 to Ia17.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-fluorophenylcarbonyloxy and R⁷ is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa18, in particular to the compounds Ia18.1 to Ia18.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-fluorophenylcarbonyloxy and R⁷ is t-butyl.

Extraordinary preference is also given to the compounds of the formulaIa19, in particular to the compounds Ia19.1 to Ia19.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-trifluoromethylphenylcarbonyloxy.

Extraordinary preference is also given to the compounds of the formulaIa20, in particular to the compounds Ia20.1 to Ia20.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-trifluoromethylphenylcarbonyloxy and R⁷ is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa21, in particular to the compounds Ia21.1 to Ia21.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-trifluoromethylphenylcarbonyloxy and R⁷ is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa22, in particular to the compounds Ia22.1 to Ia22.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-trifluoromethylphenylcarbonyloxy and R⁷ is t-butyl.

Extraordinary preference is also given to the compounds of the formulaIa23, in particular to the compounds Ia23.1 to Ia23.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-chlorophenylcarbonyloxy.

Extraordinary preference is also given to the compounds of the formulaIa24, in particular to the compounds Ia24.1 to Ia24.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-chlorophenylcarbonyloxy and R⁷ is ethyl.

Extraordinary preference is also given to the compounds of the formulaIa25, in particular to the compounds Ia25.1 to Ia25.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-chlorophenylcarbonyloxy and R⁷ is isopropyl.

Extraordinary preference is also given to the compounds of the formulaIa26, in particular to the compounds Ia26.1 to Ia26.77, which differfrom the corresponding compounds Ia1.1 to Ia1.77 in that R⁶ is3-chlorophenylcarbonyloxy and R⁷ is t-butyl.

The cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles of the formula I can be obtained by different routes,for example by the processes below.

Process A:

Compounds of the formula I where R⁶=OH are obtained by reactingpyrazoles of the formula II with an activated benzoic acid derivativeIIIα or a benzoic acid IIIβ, which is preferably activated in situ, togive the corresponding acylation product If and subsequentrearrangement.

L¹ is hydroxyl or a nucleophilically displaceable leaving group, such ashalogen, for example bromine or chlorine, hetaryl, for exampleimidazolyl or pyridyl, carboxylate, for example acetate,trifluoroacetate, etc.

The activated benzoic acid derivative can be employed directly, such asin the case of the benzoyl halides, or be generated in situ, for exampleusing dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylicester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole,etc.

It may be advantageous to carry out the acylation reaction in thepresence of a base. The reactants and the auxiliary base are in thiscase advantageously employed in equimolar amounts. A slight excess ofauxiliary base, for example from 1.2 to 1.5 molar equivalents, based onII, may be advantageous in certain cases.

Suitable auxiliary bases are tertiary alkylamines, pyridine or alkalimetal carbonates. Suitable for use as solvents are, for example,chlorinated hydrocarbons, such as methylene chloride,1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene,chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether,dimethoxyethane, tetrahydrofuran, dioxane, polar aprotic solvents, suchas acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters, suchas ethyl acetate, or mixtures of these.

If the activated carboxylic acid component used is a benzoyl halide, itmay be advantageous to cool the reaction mixture to 0-10° C. when addingthis reaction partner. The mixture is subsequently stirred at 20-100°C., preferably at 25-50° C., until the reaction has ended. Work-up iscarried out in a customary manner, for example by pouring the reactionmixture into water and extracting the product of value. Solvents whichare particularly suitable for this purpose are methylene chloride,diethyl ether, dimethoxyethane and ethyl acetate. The organic phase isdried and the solvent is removed, after which the crude ester I′ can beemployed for the rearrangement without any further purification.

The rearrangement of the esters I′ to give the compounds of the formulaI is advantageously carried out at 20-40° C. in a solvent and in thepresence of a base and, if appropriate, using a cyano compound ascatalyst.

Suitable solvents are, for example, acetonitrile, methylene chloride,1,2-dichloroethane, dioxane, ethyl acetate, dimethoxyethane,tetrahydrofuran, toluene, or mixtures of these. Preferred solvents areacetonitrile and dioxane.

Suitable bases are tertiary amines, such as triethylamine, pyridine, oralkali metal carbonates, such as sodium carbonate or potassiumcarbonate, which are preferably employed in an equimolar amount or an upto four-fold excess, based on the ester. Preference is given to usingtriethylamine or alkali metal carbonates, preferably in twice theequimolar amount, based on the ester.

Suitable cyano compounds are inorganic cyanides, such as sodium cyanideand potassium cyanide, and organic cyano compounds, such as acetonecyanohydrin and trimethylsilyl cyanide. They are employed in an amountof from 1 to 50 mol percent, based on the ester. Preference is given tousing acetone cyanohydrin or trimethylsilyl cyanide, for example in anamount of from 5 to 15, preferably 10, mol percent, based on the ester.

Work-up can be carried out in a manner known per se. The reactionmixture is, for example, acidified with dilute mineral acid, such as 5%strength hydrochloric acid or sulfuric acid, and extracted with anorganic solvent, for example methylene chloride or ethyl acetate. Theorganic extract can be extracted with 5-10% strength alkali metalcarbonate solution, for example sodium carbonate or potassium carbonatesolution. The aqueous phase is acidified and the resulting precipitateis filtered off with suction and/or extracted with methylene chloride orethyl acetate, and the mixture is dried and concentrated. (Examples ofthe preparation of esters of hydroxypyrazoles and of the rearrangementof the esters are given, for example, in EP-A 282 944 and U.S. Pat. No.4,643,757).

However, it is also possible to generate the ester I′ in situ byreacting a pyrazole of the formula II or an alkali metal salt thereofwith a cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)benzene derivativeof the formula IV in the presence of carbon monoxide, a catalyst and abase.

L² is a leaving group, such as halogen, for example chlorine, bromine oriodine, or sulfonate, such as mesylate or triflate; preference is givento bromine or triflate.

If appropriate, the ester I′ is converted directly into thecyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazole of the formula I.

Suitable catalysts are palladium-ligand complexes in which the palladiumis present in the oxidation stage 0, metallic palladium, which hasoptionally been absorbed on a support, and preferably palladium(II)salts. The reaction with palladium(II) salts and metallic palladium ispreferably carried out in the presence of complex ligands.

An example of a suitable palladium(0) ligand complex istetrakis(triphenylphosphine)palladium.

Metallic palladium is preferably absorbed on an inert support such as,for example, activated carbon, silica, alumina, barium sulfate orcalcium carbonate. The reaction is preferably carried out in thepresence of complex ligands such as, for example, triphenylphosphine.

Examples of suitable palladium(II) salts are palladium acetate andpalladium chloride. The presence of complex ligands such as, forexample, triphenylphosphine is preferred.

Suitable complex ligands for the palladium-ligand complexes, or in whosepresence the reaction with metallic palladium or palladium(II) salts ispreferably carried out, are tertiary phosphines whose structure isrepresented by the following formulae:

where z is 1 to 4 and the radicals R^(a) to R^(g) are C₁-C₆-alkyl,C₃-C₆-cycloalkyl, aryl-C₁-C₂-alkyl or, preferably, aryl. Aryl is, forexample, naphthyl and unsubstituted or substituted phenyl such as, forexample, 2-tolyl and, in particular, unsubstituted phenyl.

The complex palladium salts can be prepared in a manner known per sestarting from commercially available palladium salts such as palladiumchloride or palladium acetate and the appropriate phosphines, such as,for example, triphenylphosphine, tricyclohexylphosphine or1,2-bis(diphenylphosphino)ethane. Many of the complexed palladium saltsare also commercially available. Preferred palladium salts are[(R)(+)2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]palladium(II)chloride, bis(triphenylphosphine)palladium(II) acetate and, inparticular, bis(triphenylphosphine)palladium(II) chloride.

The palladium catalyst is usually employed in a concentration of from0.05 to 5 mol %, and preferably 1-3 mol %.

Suitable bases are tertiary amines, such as, for example,N-methylpiperidine, ethyldiisopropylamine,1,8-bisdimethylaminonaphthalene or, in particular, triethylamine. Alsosuitable is alkali metal carbonate, such as sodium carbonate orpotassium carbonate. However, mixtures of potassium carbonate andtriethylamine are also suitable.

In general, from 2 to 4 molar equivalents, in particular 2 molarequivalents, of the alkali metal carbonate, and from 1 to 4 molarequivalents, in particular 2 molar equivalents, of the tertiary amineare employed, based on the cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)benzene derivative of the formula IV.

Suitable solvents are nitrites, such as benzonitrile and acetonitrile,aromatic hydrocarbons, such as toluene, amides, such asdimethylformamide, dimethylacetamide, tetra-C₁-C₄-alkylureas orN-methylpyrrolidone and, preferably, ethers, such as tetrahydrofuran andmethyl tert-butyl ether. Particular preference is given to ethers, suchas 1,4-dioxane and dimethoxyethane, as solvents.

The compounds of the formula IIIb can be obtained, for example, asfollows:

The oximes of the formula V can be converted into the4,5-dihydroisoxazol-3-yl-benzene derivatives VI in a manner known per sevia the hydroxamic acid halide, in particular hydroxamic acid chloride,intermediates. From these, nitrile oxides are prepared in situ, andthese nitrile oxides react with alkenes to give the desired products(cf., for example, Chem. Ber. 106 (1973), 3258-3274). Thus, for example,the oxime V is oxidized using sodium hypochlorite and reacted with anallyl halide, for example allyl chloride, in an inert solvent, such asmethylene chloride, chloroform, tetrahydrofuran, dioxane oracetonitrile, to give the (4,5-dihydroisoxazol-3-yl)benzene derivativeVI. This is then reacted in the presence of a catalyst and a base withcarbon monoxide and water to give VII.

L² is a leaving group, such as halogen, for example chlorine, bromine oriodine, or sulfonate, such as mesylate or triflate; preference is givento bromine or triflate.

X is halogen, preferably chlorine or bromine.

Suitable catalyst systems are the palladium-ligand complexes describedabove. The reaction conditions are similar.

Ring closure of the cyclopropane ring, i.e. conversion of the compoundVII into the compound IIIβ, is carried out using strong bases, such asalkali metal alkoxides, for example potassium tert-butoxide, preferablyin polar aprotic solvents, such as dimethyl sulfoxide.

Ring closure of the cyclopropane ring can also be carried out at thestage of the compound VI giving the compound IV, which can be reactedfurther in a similar manner using carbon monoxide and water in thepresence of a catalyst and base to give IIIβ.

It is also possible to obtain the compounds of the formula IIIβ byconverting an oxime of the formula VIII into the correspondinghydroxamic acid halide, in particular hydroxamic acid chloride,generating a nitrile oxide in situ and reacting this with an alkene(cf., for example, Chem. Ber. 106 (1973), 3258-3274). The ester is thenhydrolyzed under conditions known per se to give the(4,5-dihydroisoxazol-3-yl)benzene VII and reacted further as describedabove.

L³ is a C₁-C₆-alkoxy radical and X is halogen, preferably chlorine orbromine.

Compounds of the formula I where R⁶‡hydroxyl are obtained by reactingcompounds of the formula I where R⁶=hydroxyl with alkylating agents,sulfonylating agents or acylating agents L⁴—R^(6a)(X).

L⁴ is a nucleophilically displaceable leaving group, such as halogen,for example bromine or chlorine, acyloxy, for example acetyloxy orethylcarbonyloxy, or alkylsulfonyloxy, for example methylsulfonyloxy ortrifluoromethylsulfonyloxy.

R^(6a)is C₁-C₆-alkyl, C₃-C₆-alkenyl, C₁-C₆-alkylsulfonyl,C₁-C₆-alkylcarbonyl, phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C₄-alkyl,phenylsulfonyl or phenylcarbonyl, where the phenyl radical of the fourlastmentioned substituents may be partially or fully halogenated and/ormay carry one to three of the following groups: nitro, cyano,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.

The compounds of the formula X can be employed directly, such as, forexample, in the case of the sulfonyl halides or sulfonic anhydrides, orbe generated in situ, for example activated sulfonic acids (usingsulfonic acid and dicyclohexylcarbodiimide, carbonyldiimidazole, etc.).

The starting materials are generally employed in an equimolar ratio.However, it may also be advantageous to employ an excess of one or theother component.

If appropriate, it may be advantageous to carry out the reaction in thepresence of a base. The reactants and the auxiliary base areadvantageously employed in equimolar amounts. An excess of auxiliarybase, for example from 1.5 to 3 molar equivalents, based on I (whereR⁶=OH), may be advantageous in certain cases.

Suitable auxiliary bases are tertiary alkylamines, such astriethylamine, pyridine, alkali metal carbonates, for example sodiumcarbonate, potassium carbonate, and alkali metal hydrides, for examplesodium hydride. Preference is given to using triethylamine and pyridine.

Suitable solvents are, for example, chlorinated hydrocarbons, such asmethylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, forexample toluene, xylene, chlorobenzene, ethers, such as diethyl ether,methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aproticsolvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide,or esters, such as ethyl acetate, or mixtures of these.

In general, the reaction temperature is in the range from 0° C. to theboiling point of the reaction mixture.

Work-up can be carried out in a manner known per se to give the product.

The pyrazoles of the formula II are known or can be prepared byprocesses known per se (for example EP-A 240 001 and J. Prakt. Chem. 315(1973), 383).

The compounds of the formulae III and IV as such are in each case novel

where in each case the variables R¹ to R⁵ are as defined under thecompounds of the formula I and

L is hydroxyl or a radical which can be removed by hydrolysis; and

L² is a nucleophilically displaceable leaving group.

Examples of radicals which can be removed by hydrolysis are alkoxy,phenoxy, alkylthio and phenylthio radicals which may be substituted orunsubstituted, halides, hetaryl radicals attached via nitrogen, aminoand imino radicals which may be substituted or unsubstituted, etc.

Examples of nucleophilically displaceable leaving groups are halogen,C₁-C₄-alkylsulfonyloxy and C₁-C₄-haloalkylsulfonyloxy.

Preferred compounds of the formula III are those in which L is halogen,in particular chlorine or bromine.

Preference is also given to those compounds of the formula III in whichL is hydroxyl.

Preference is also given to those compounds of the formula III in whichL is C₁-C₆-alkoxy.

With respect to the variables R¹ to R⁵, the particularly preferredembodiments of the compounds of the formulae III and IV correspond tothose of the cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzenepyrazoles of the formula I.

Process B:

Alternatively, the compounds of the formula I where R⁶=OH can beprepared as follows:

Suitable bases and solvents are those mentioned above for the ringclosure.

The compounds of the formula I where R⁶=OH can be converted as discussedabove by reaction with alkylating agents, sulfonylating agents oracylating agents L⁴—R^(6a)(X) into compounds of the formula I whereR⁶=OH.

PREPARATION EXAMPLES4-[2-Methyl-3-(2-oxa-3-azabicyclo[3.1.0]hex-3-en-4-yl)-4-methyl-sulfonylbenzoyl]-5-hydroxy-1-methyl-1H-pyrazole(compound 2.3)

Step a)

At 15-20° C., 3.04 g of potassium tert-butoxide were added to a solutionof 3.0 g (9 mmol) of2-methyl-3-(5-chloromethyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoicacid in 5 ml of dimethyl sulfoxide, and the mixture was stirred at roomtemperature overnight. The reaction mixture was stirred into 0.3 l of 3%strength hydrochloric acid and extracted three times with ethyl acetate.The combined organic phases were washed with water and dried, and thesolvent was removed. The residue was purified by silica gel columnchromatography (mobile phase=toluene/tetrahydrofuran/acetic acid 8/2/1).This gave 1.3 g (49% of theory) of2-methyl-3-(2-oxa-3-azabicyclo[3.1.0]hex-3-en-4-yl)-4-methylsulfonylbenzoicacid. The ¹H-NMR spectrum corresponded to the given structure.

Step b)

Under an atmosphere of nitrogen, 0.79 g (3.9 mmol) ofdicyclohexylcarbodiimide was added to a solution of 0.75 g (2.54 mmol)of the product from step a) and 0.25 g (2.54 mmol) of1-methyl-5-hydroxy-1H-pyrazole in 50 ml of anhydrous acetonitrile, andthe mixture was stirred at 40° C. for 2 hours and at room temperaturefor a further 12 hours. The solvent was evaporated under reducedpressure and the residue was taken up in ethyl acetate, extracted threetimes with 5% strength potassium carbonate solution, washed three timeswith water, dried and concentrated to dryness. This gave 1.2 g of aviscous brown oil which was reacted further without purification.

Step c)

A mixture of 1.2 g of the product from step b) and 0.52 g of potassiumcarbonate in 5 ml of dioxane was stirred at room temperature for 4hours. The mixture was then concentrated to dryness under reducedpressure, the residue was taken up in water and the aqueous phase waswashed three times with diethyl ether. The pH of the aqueous phase wasthen adjusted to 1-2 using 10% strength hydrochloric acid and theaqueous phase was extracted three times with ethyl acetate. The combinedorganic phases were washed with water, dried and concentrated to drynessunder reduced pressure. This gave 0.3 g (33% of theory) of an amorphousfoam. The ¹H-NMR spectrum corresponded to the given structure of thetitle compound.

4-[2-Methyl-3-(2-oxa-3-aza-bicyclo[3.1.0]hex-3-en-4-yl)-4-methylsulfonylbenzoyl]-5-hydroxy-1-tert-butyl-1H-pyrazole(compound 2.1)

At room temperature, 0.17 g (1.50 mmol) of potassium tert-butoxide wasadded to a solution of 0.23 g (0.51 mmol) of4-[2-methyl-3-(5-chloromethyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-5-hydroxy-1-tert-butyl-1H-pyrazolein 2.5 ml of dimethyl sulfoxide, and the mixture was stirred overnight.The mixture was then stirred into 300 ml of 3% strength aqueoushydrochloric acid, the aqueous phase was extracted three times with ineach case 200 ml of ethyl acetate and the combined organic phases werewashed four times with in each case 50 ml of water, dried over sodiumsulfate and concentrated under reduced pressure. This gave 0.12 g (57%)of the title compound in the form of a brown solid of melting point69-74° C.

¹H-NMR (δ in ppm): δ=1.1-1.3 (m, 2H), 1.58 (s, 9H), 2.58 (s, 3H),2.3-2.5 (m, 1H), 3.22 (s, 3H), 5.21 (m, 1H), 7.32 (s, 1H), 7.72 (d, 1H),8.11 (d, 1H).

In addition to the compound above, Table 2 lists furthercyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles of the formula I which were prepared or are preparablein a similar manner.

TABLE 2

Physical data No. R¹ R² R³ R⁴ R⁵ R⁶ R⁷ R⁸ m.p. [° C.] 2.1 CH₃ SO₂CH₃ H HH OH C(CH₃)₃ H 69-74 2.2 CH₃ SO₂CH₃ H H H OH C₂H₅ H 94-97 2.3 CH₃ SO₂CH₃H H H OH CH₃ H 106-112 2.4 CH₃ SO₂CH₃ H H H OH CH(CH₃)₂ H 90-95 2.5 CH₃SO₂CH₃ H H H OH CH₃ CH₃ 89-91 2.6 CH₃ SO₂CH₃ H CH₂Cl H OH CH₂CH₃ H 99-103 2.7 CH₃ SO₂CH₃ H CH₃ H OH CH₃ H  98-102 2.8 CH₃ SO₂CH₃ H —CH₂—OH CH(CH₃)₂ H 115-119 2.9 CH₃ SO₂CH₃ H —CH₂— OH C(CH₃)₃ H 136-140 2.10CH₃ SO₂CH₃ H CH₃ H OH C(CH₃)₃ H 90-95 2.11 CH₃ SO₂CH₃ H CH₃ H OHCH(CH₃)₂ H 67-70 2.12 CH₃ SO₂CH₃ H CH₃ H OH cyclo-C₃H₅ H 71-79 2.13 CH₃SO₂CH₃ H H CH₃ OH CH₃ H  99-103 2.14 CH₃ SO₂CH₃ H H CH₃ OH CH(CH₃)₂ H75-80 2.15 CH₃ SO₂CH₃ H H CH₃ OH cyclo-C₃H₅ H 65-70 2.16 CH₃ SO₂CH₃ H HCH₃ OH C(CH₃)₃ H 110-115

The cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles of the formula I and their agriculturally useful saltsare suitable, both in the form of isomer mixtures and in the form of thepure isomers, as herbicides. The herbicidal compositions comprisingcompounds of the formula I control vegetation on non-crop areas veryefficiently, especially at high rates of application. They act againstbroad-leaved weeds and harmful grasses in crops such as wheat, rice,maize, soya and cotton without causing any significant damage to thecrop plants. This effect is mainly observed at low rates of application.

Depending on the application method used, the compounds of the formulaI, or herbicidal compositions comprising them, can additionally beemployed in a further number of crop plants for eliminating undesirableplants. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica),Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharumofficinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds of the formula I may also be used in cropswhich tolerate the action of herbicides owing to breeding, includinggenetic engineering methods.

The compounds of the formula I, or the herbicidal compositionscomprising them, can be used for example in the form of ready-to-sprayaqueous solutions, powders, suspensions, also highly-concentratedaqueous, oily or other suspensions or dispersions, emulsions, oildispersions, pastes, dusts, materials for broadcasting or granules, bymeans of spraying, atomizing, dusting, broadcasting or watering. The useforms depend on the intended aims; in any case, they should ensure avery fine distribution of the active compounds according to theinvention.

The herbicidal compositions comprise a herbicidally effective amount ofat least one compound of the formula I or an agriculturally useful saltof I and auxiliaries customarily used for formulating crop protectionagents.

Essentially, suitable inert auxiliaries include: mineral oil fractionsof medium to high boiling point, such as kerosene and diesel oil,furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins,tetrahydronaphthalene, alkylated naphthalenes and their derivatives,alkylated benzenes and their derivatives, alcohols such as methanol,ethanol, propanol, butanol and cyclohexanol, ketones such ascyclohexanone, or strongly polar solvents, e.g. amines such asN-methylpyrrolidone, and water.

Aqueous use forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes or oil dispersions, thecyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles, either as such or dissolved in an oil or solvent, canbe homogenized in water by means of a wetting agent, tackifier,dispersant or emulsifier. Alternatively, it is possible to prepareconcentrates consisting of active substance, wetting agent, tackifier,dispersant or emulsifier and, if desired, solvent or oil, which aresuitable for dilution with water.

Suitable surfactants (adjuvants) are the alkali metal salts, alkalineearth metal salts and ammonium salts of aromatic sulfonic acids, e.g.ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, andof fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, laurylether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-,hepta- and octadecanols, and also of fatty alcohol glycol ethers,condensates of sulfonated naphthalene and its derivatives withformaldehyde, condensates of naphthalene, or of the naphthalenesulfonicacids with phenol and formaldehyde, polyoxyethylene octylphenol ether,ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl ortributylphenyl polyglycol ether, alkylaryl polyether alcohols,isotridecyl alcohol, fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylenealkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters,lignosulfite waste liquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor grinding the active substances together with a solid carrier.

Granules, e.g. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active compounds to solidcarriers. Solid carriers are mineral earths, such as silicas, silicagels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers such asammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, andproducts of vegetable origin, such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders, or other solid carriers.

The concentrations of the compounds of the formula I in the ready-to-usepreparations can be varied within wide ranges. In general, theformulations comprise from about 0.001 to 98% by weight, preferably from0.01 to 95% by weight of at least one active compound. The activecompounds are employed in a purity of from 90% to 100%, preferably from95% to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, forexample, as follows:

I. 20 parts by weight of the compound No. 2.5 are dissolved in a mixtureconsisting of 80 parts by weight of alkylated benzene, 10 parts byweight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleicacid N-monoethanolamide, 5 parts by weight of calciumdodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol ofethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000parts by weight of water and finely distributing it therein gives anaqueous dispersion which comprises 0.02% by weight of the activecompound.

II. 20 parts by weight of the compound No. 2.5 are dissolved in amixture consisting of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 mol ofethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of theadduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring thesolution into 100,000 parts by weight of water and finely distributingit therein gives an aqueous dispersion which comprises 0.02% by weightof the active compound.

III. 20 parts by weight of the active compound No. 2.5 are dissolved ina mixture consisting of 25 parts by weight of cyclohexanone, 65 parts byweight of a mineral oil fraction of boiling point 210 to 280° C. and 10parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol ofcastor oil. Pouring the solution into 100,000 parts by weight of waterand finely distributing it therein gives an aqueous dispersion whichcomprises 0.02% by weight of the active compound.

IV. 20 parts by weight of the active compound No. 2.5 are mixedthoroughly with 3 parts by weight of sodiumdiisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt ofa lignosulfonic acid from a sulfite waste liquor and 60 parts by weightof pulverulent silica gel, and the mixture is ground in a hammer mill.Finely distributing the mixture in 20,000 parts by weight of water givesa spray mixture which comprises 0.1% by weight of the active compound.

V. 3 parts by weight of the active compound No. 2.5 are mixed with 97parts by weight of finely divided kaolin. This gives a dust whichcomprises 3% by weight of the active compound.

VI. 20 parts by weight of the active compound No. 2.5 are mixedintimately with 2 parts by weight of the calcium salt ofdodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycolether, 2 parts by weight of the sodium salt of aphenol/urea/formaldehyde condensate and 68 parts by weight of aparaffinic mineral oil. This gives a stable oily dispersion.

VII. 1 part by weight of the active compound No. 2.5 is dissolved in amixture consisting of 70 parts by weight of cyclohexanone, 20 parts byweight of ethoxylated isooctylphenol and 10 parts by weight ofethoxylated castor oil. This gives a stable emulsion concentrate.

VIII. 1 part by weight of the active compound No. 2.5 is dissolved in amixture consisting of 80 parts by weight of cyclohexanone and 20 partsby weight of Wettol® EM 31 (nonionic emulsifier based on ethoxylatedcastor oil). This gives a stable emulsion concentrate.

The compounds of the formula I or the herbicidal compositions can beapplied pre- or post-emergence. If the active compounds are less welltolerated by certain crop plants, application techniques may be used inwhich the herbicidal compositions are sprayed, with the aid of thespraying equipment, in such a way that they come into contact as littleas possible, if at all, with the leaves of the sensitive crop plants,while the active compounds reach the leaves of undesirable plantsgrowing underneath, or the bare soil surface (post-directed, lay-by).

The application rates of the compound of the formula I are from 0.001 to3.0, preferably from 0.01 to 1.0 kg/ha of active substance (a.s.),depending on the control target, the season, the target plants and thegrowth stage.

To widen the activity spectrum and to achieve synergistic effects, thecyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles of the formula I may be mixed with a large number ofrepresentatives of other herbicidal or growth-regulating active compoundgroups and then applied concomitantly. Suitable components for mixturesare, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides,aminophosphoric acid and its derivatives, aminotriazoles, anilides,(het)aryloxyalkanoic acids and their derivatives, benzoic acid and itsderivatives, benzothiadiazinones, 2-(het)aroyl-1,3-cyclohexanediones,hetaryl aryl ketones, benzylisoxazolidinones, meta-CF₃-phenylderivatives, carbamates, quinolinecarboxylic acid and its derivatives,chloroacetanilides, cyclohexenone oxime ether derivatives, diazines,dichloropropionic acid and its derivatives, dihydrobenzofurans,dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers,dipyridyls, halocarboxylic acids and their derivatives, ureas,3-phenyluracils, imidazoles, imidazolinones,N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols,aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid andits derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles,phenylpyrazoles, pyridazines, pyridinecarboxylic acid and itsderivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines,triazinones, triazolinones, triazolecarboxamides and uracils.

It may furthermore be advantageous to apply the compounds of the formulaI, alone or else concomitantly in combination with other herbicides, orin the form of a mixture with other crop protection agents, for exampletogether with agents for controlling pests or phytopathogenic fungi orbacteria. Also of interest is the miscibility with mineral saltsolutions, which are employed for treating nutritional and trace elementdeficiencies. Non-phytotoxic oils and oil concentrates may also beadded.

USE EXAMPLES

The herbicidal activity of the cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formulaI was demonstrated by the following greenhouse experiments:

The cultivation containers used were plastic pots containing loamy sandwith approximately 3.0% of humus as the substrate. The seeds of the testplants were sown separately for each species.

For the pre-emergence treatment, directly after sowing the activecompounds, which had been suspended or emulsified in water, were appliedby means of finely distributing nozzles. The containers were irrigatedgently to promote germination and growth and subsequently covered withtransparent plastic hoods until the plants had rooted. This cover causeduniform germination of the test plants, unless this was adverselyaffected by the active compounds.

For the post-emergence treatment, the test plants were first grown to aheight of from 3 to 15 cm, depending on the plant habit, and only thentreated with the active compounds which had been suspended or emulsifiedin water. The test plants were for this purpose either sown directly andgrown in the same containers, or they were first grown separately asseedlings and transplanted into the test containers a few days prior totreatment. The application rate for the post-emergence treatment was0.25 or 0.125 kg of a.s. (active substance)/ha.

Depending on the species, the plants were kept at 10-25° C. or 20-35° C.The test period extended over from 2 to 4 weeks. During this time, theplants were tended, and their response to the individual treatments wasevaluated.

The evaluation was carried out using a scale from 0 to 100. 100 means noemergence of the plants, or complete destruction of at least the aerialparts and 0 means no damage, or normal course of growth.

The plants used in the greenhouse experiments were of the followingspecies:

Scientific name Common name Amaranthus retroflexus pig weed Avena fatuawild oat Chenopodium album lambsquaters Echinochloa crus gallibarnyardgrass Polygonum persicaria ladysthumb Setaria faberi giantfoxtail

At application rates of 0.25 or 0.125 kg/ha, the compound No. 2.5 (Table2) showed very good post-emergence action against the abovementionedundesirable plants.

We claim:
 1. A cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazole of the formulaI

in which R¹ is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy,C₁-C₆-haloalkoxy, halogen or nitro; R² is C₁-C₆-alkyl, C₁-C₆-haloalkyl,C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkylthio, C₁-C₆-haloalkylthio,C₁-C₆-alkylsulfinyl, C₁-C₆-haloalkylsulfinyl, C₁-C₆-alkylsulfonyl,C₁-C₆-haloalkylsulfonyl, halogen, cyano or nitro; R³ is hydrogen,C₁-C₆-alkyl or halogen; R⁴ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;R⁵ may have the meanings given for R⁴; or R⁴, R⁵ together are aC₁-C₄-alkanediyl group which may be partially or fully halogenatedand/or may carry one to three C₁-C₄-alkyl groups; R⁶ is hydroxyl,C₁-C₆-alkoxy, C₃-C₆-alkenyloxy, C₁-C₆-alkylsulfonyloxy,C₁-C₆-alkylcarbonyloxy, phenyl-C₁-C₄-alkoxy,phenylcarbonyl-C₁-C₄-alkoxy, phenylsulfonyloxy, phenylcarbonyloxy, wherethe phenyl radical of the four lastmentioned substituents may bepartially or fully halogenated and/or may carry one to three of thefollowing groups: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₁-C₄-alkoxy or C₁-C₄-haloalkoxy; R⁷ is hydrogen, C₁-C₆-alkyl orcyclopropyl; R⁸ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl; and itsagriculturally useful salts.
 2. A cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazole as claimed inclaim 1 in which R¹ is C₁-C₆-alkyl or halogen; R² is C₁-C₆-haloalkyl,C₁-C₆-alkylsulfonyl or halogen; R³ is hydrogen, C₁-C₄-alkyl or halogen;R⁷ is C₁-C₄-alkyl or cyclopropyl; R⁸ is hydrogen or C₁-C₄-alkyl.
 3. Acyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazole as claimed in claim 1 in which R⁶ is hydroxyl,phenyl-C₁-C₂-alkoxy, phenylcarbonyl-C₁-C₂-alkoxy, phenylsulfonyloxy orphenylcarbonyloxy, where the phenyl radical of the four lastmentionedsubstituents may be partially or fully halogenated and/or may carry oneto three of the following groups: nitro, cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.
 4. A process forpreparing cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles as claimed in claim 1, which comprises acylating apyrazole of the formula II

with a benzoic acid derivative of the formula III,

in which the variables R¹ to R⁵, R⁷ and R⁸ are as defined in claim 1 andL¹ is hydroxyl or a nucleophilically displaceable leaving group;rearranging the acylation product to form a compound of the formula I inwhich R⁶ is hydroxyl and, if appropriate, reacting the product of therearrangement with a compound of the formula X L⁴—R^(6a)  X  in which L⁴is a nucleophilically displaceable leaving group; and R^(6a) isC₁-C₆-alkyl, C₃-C₆-alkenyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylcarbonyl,phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C₄-alkyl, phenylsulfonyl orphenylcarbonyl, where the phenyl radical of the four lastmentionedsubstituents may be partially or fully halogenated and/or may carry oneto three of the following groups: nitro, cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.
 5. A process forpreparing cyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazoles as claimed in claim 1, which comprises reacting apyrazone of the formula II

in which the variables R⁷ and R⁸ are as defined in claim 1, or an alkalimetal salt thereof, with a cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-benzene derivative IV

where the variables R¹ to R⁵ are as defined in claim 1 and L² is aleaving group in the presence of carbon monoxide, a catalyst and a baseand, if appropriate, reacting the condensation product with a compoundof the formula X L⁴—R^(6a)  X in which L⁴ and R^(6a) are as defined inclaim
 4. 6. A process for preparing cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles as claimed inclaim 1, which comprises reacting a3-(5-halomethyl-4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazole ofthe formula XI

in which R¹ to R⁵, R⁷ and R⁸ are as defined in claim 1 and X is halogenwith a base to give a compound of the formula I in which R⁶ is hydroxyland, if appropriate, reacting the reaction product with a compound ofthe formula X L⁴—R^(6a)  X in which L⁴ and R^(6a) are as defined belowL⁴ is a nucleophilically displaceable leaving group; and R^(6a) isC₁-C₆-alkyl, C₃-C₆-alkenyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylcarbonyl,phenyl-C₁-C₄-alkyl, phenylcarbonyl-C₁-C₄-alkyl, phenylsulfonyl orphenylcarbonyl, where the phenyl radical of the four lastmentionedsubstituents may be partially or fully halogenated and/or may carry oneto three of the following groups: nitro cyano, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.
 7. A compound of theformula III or IV

in which R¹ to R⁵ are as defined in claim 1, L is hydroxyl or a radicalwhich can be removed by hydrolysis and L² is a nucleophilicallydisplaceable leaving group.
 8. A composition, comprising a herbicidallyeffective amount of at least one cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazole of the formulaI or an agriculturally useful salt thereof as claimed in claim 1 andauxiliaries customarily used for formulating crop protection agents. 9.A method for controlling undesirable vegetation, which comprisesallowing a herbicidally effective amount of at least onecyclopropyl-fused 3-(4,5-dihydroisoxazol-3-yl)-substitutedbenzoylpyrazole of the formula I or an agriculturally useful saltthereof as claimed in claim 1 to act on plants, their habitat and/or onseeds.
 10. A herbicide containing cyclopropyl-fused3-(4,5-dihydroisoxazol-3-yl)-substituted benzoylpyrazoles of the formulaI and/or agriculturally useful salts thereof as claimed in claim 1.